Color photographic material

ABSTRACT

A color photographic material comprising a support and at least one layer thereon containing at least one compound of formula [I]: Formula [I] ##STR1## wherein R 1  R 2 , R 3 , R 4 , R 5  and R 6  each are defined in the specification and claims of this application. 
     The compound of formula [I] is incorporated in a color photographic material to prevent the discoloration and fading-in-color of the color photographic material.

This is a division of application Ser. No. 939,968 filed Sept. 6, 1978.

This invention relates to a color photographic material. Moreparticularly, it relates to a color photographic material in which areprevented discoloration and color-fading caused by light in a dye imagepart and an unexposed part obtained by processing a light-sensitivesilver halide color photographic material.

It is well-known that color images are formed by the reaction ofcouplers with an oxidation product of an aromatic primary amine, whichproduct was produced by developing exposed silver halide grains in alight sensitive silver halide color photographic material by using anaromatic primary amine.

In this process, there have usually been used a compound having anopen-chain active methylene group as a yellow coupler for forming ayellow dye; a compound having a pyrazolone, pyrazolinobenzimidazole,indazolone or pyrazolotriazole nucleus in which is comprised aclosed-chain methylene group as a magenta coupler for forming a amagenta dye. All of these compounds forms azomethine dyes by thereaction with an oxidation product of an aromatic primary amine. As acyan coupler for forming a cyan dye, there have generally been usedphenols or α-naphthols having a phenolic hydroxyl group which formindoaniline type dyes by the reaction with an oxidation product of anaromatic primary amine.

It is desired that the dye images obtained from such couplers are stableeven at high temperature or humidity, and do not discolor and fade incolor when exposed to light for a long period of time. But theirfastness (referred to as light resistance) mainly against ultravioletrays or visible ray have not been satisfactory yet and it is known thatirradiation by actinic rays dye images causes comparatively easydiscoloration. To avoid such defects, there have been known variousmethods for improving the light resistance by using couplers with asmaller amount of discoloration; by using a ultraviolet absorber toprotect dye images from ultraviolet ray; by adding anti-fading agent toprevent the fading by light; or by introducing a group which giveslight-resistance into a coupler molecule. But for obtaining satisfactorylight resistance of the dye images by using ultraviolet absorbers, arelatively large amount of them is needed and often results in stainingof dye images due to coloration from the ultraviolet absorbersthemselves. Using ultraviolet absorbers also has no effect onanti-fading of dye images due to visible light and has a limit forimproving the light resistance with ultraviolet absorbers. There havefurther been known various anti-fading agents for dye images which havetherein a phenolic hydroxyl group or a group producing a phenolichydroxyl group when subject to hydrolysis. For example, in JapanesePatent Publications Nos. 31256/1973, 31625/1973 and 30462/1976, andJapanese Laid Open to Public Patent Publication Nos. 134326/1974 and134327/1974 have been proposed phenols and bisphenols; pyrogallol,garlic acid and its esters in U.S. Pat. No. 3,069,262; α-tocopherols andtheir acyl derivatives in U.S. Pat. Nos. 2,360,290 and 4,015,990;hydroquinone derivatives in Japanese Patent Publication No. 27534/1977,Japanese Laid Open to Public Patent Publication No. 4751/1977 and U.S.Pat. No. 2,735,765; 6-hydroxychromans in U.S. Pat. Nos. 3,432,300 and3,574,627; 5-hydroxy-cumarans in U.S. Pat. No. 3,573,050; and6,6'-dihydroxy-2,2'-bisspirochromans in Japanese Patent Publication No.20977/1974.

Although these compounds have some effect on the light resistance of dyeimages, their effects is not sufficient. The anti-fading effect isreduced or extinguished rapidly at a certain time during thepreservation of a color photographic material for a long period of time.Furthermore, in some cases, the so-called after-yellowing (hereinaftercalled "Y-stain") owing to the actinic ray is brought about in theportions of the processed color photographic material where unreactedcouplers remain, i.e. unexposed areas of the material. Some of thesecompounds have little solubility in the solvent used when they are addedto a color photographic material. Due to the diffusibility, some ofthese compounds diffuse into a processing solution having high pH value.Although some of these compounds show an anti-fading effect on the colordye images obtained from yellow and cyan couplers, they do not show anyanti-fading effect on the color dye images obtained from magentacouplers. Some of these compounds have no effect on the color dye imageobtained from yellow and cyan couplers or sometimes accelerate thefading, although they have relatively excellent anti-fading effect onthe color dye images obtained from megenta couplers. In thespecifications of Japanese Laid Open to Public Patent Publication(hereinafter referred to as JLOP) Nos. 37636/1972 and 20723/1975, U.S.Pat. Nos. 3,519,429 and 3,880,661, there have been proposed couplers inwhich a group giving light resistance is introduced into the molecule.These couplers, however, are disadvantageous in that, although they areeffective against ultraviolet ray, they show insufficient anti-fadingeffect against visible ray; and since they are unstable in a highlyalkaline solution such as a color developer, side-reactions occur.Further, they are insufficient in properties important to colorphotography, i.e., the properties of the couplers themselves; colordevelopability, solubility in an organic solvent, dispersion-stabilityin a silver halide emulsion, color density, etc. The light-absorptionbands sometimes shift from the desired range of wave length.Inconvenience is caused because of the undesirable ratio of the couplerpart and the anti-fading part. Further, the syntheses of these couplersrequire very complicated procedure, it is difficult to apply thesecouplers practically. Thus, these couplers are not satisfactory at thistime.

The object of this invention is to provide a color photographic materialwhich comprises an anti-fading agent which possesses an excellentanti-fading effect, an excellent solubility in a high-boiling solvent,etc., an excellent dispersion-stability and an excellentnon-diffusibility; does not affect badly other photographic additives;and does not cause the inhibition of coloration of couplers.

As a result of extensive research, the present inventors have found thatthe above mentioned object can be accomplished by using a colorphotographic material comprising a layer containing at least onecompound represented by following formula [I]: ##STR2## Wherein R₁ andR₂ each represent an alkyl group, an alkenyl group, a cycloalkyl group,an aryl group or a heterocyclic ring; R₃, R₄, R₅ and R₆ each representhydrogen or halogen, or an alkyl group, an alkenyl group, a cycloalkylgroup, an aryl group, an alkoxy group, an alkylthio group, an aryloxygroup, an arylthio group, an acyl group, an acylamino group, analkylamino group, an alkoxycarbonyl group or a sulfonamido group; andwhen both of R₁ and R₂ are alkyl groups, the total carbon number of thealkyl groups is not less than 3.

In formula [I], the halogen may be fluorine, chlorine, bromine oriodine; the alkyl group may be a straight-chain or branched one havingpreferably 1 to 32 carbon atoms, e.g., methyl, ethyl, n-butyl, t-butyl,2-ethylhexyl, 3,5,5-trimethylhexyl, 2,2-dimethylpentyl, n-octyl,t-octyl, n-dodecyl, sec-dodecyl, n-hexadecyl, n-octadecyl, eicosyl,etc., the alkenyl group may be a straight-chain or branched one havingpreferably 2 to 32 carbon atoms, e.g., allyl, butenyl, octenyl, oleyl,etc.; the cycloalkyl group may preferably contain 5 to 7 ring members,e.g., cyclopentyl, cyclohexyl, cycloheptyl, etc.; the aryl group may beexemplified by phenyl, naphthyl, etc.; the heterocyclic ring maypreferably be a 5 or 6-membered heterocyclic ring having one or morenitrogen, oxygen and/or sulfur atoms, e.g., furyl, pyranyl,tetrahydropyranyl, imidazolyl, pyrrollyl, pyrimidyl, pyradinyl,triazinyl, thienyl, quinolyl, oxazolyl, thiazolyl pyridyl, etc.

As the alkoxy group (preferably 1 to 32 carbon atoms) may be mentionedfor example methoxy, ethoxy, n-propoxy, t-butoxy, n-hexoxy, n-dodecoxy,n-octadecoxy, n-docosoxy, etc.; as the alkylthio group, e.g.,methylthio, n-butylthio, n-octylthio, n-dodecylthio, n-docosylthio,etc.; as the aryloxy group, e.g., phenoxy, naphthoxy, etc.; as thearylthio group, e.g., phenylthio etc.; as the acyl group, e.g., acetyl,butanoyl, octanoyl, dodecanoyl, benzoyl, cinnamoyl or naphthoyl, etc.;as the acylamino group, e.g., acetylamino, octanoylamino, benzoylamino,etc.; as the alkylamino group, mono- or dialkylamino such asmethylamino, ethylamino, diethylamino, isopropylamino, di-n-octylamino,di-n-decylamino, etc.; as the alkoxycarbonyl group, e.g.,methoxylcarbonyl, ethoxycarbonyl, n-nonyloxycarbonyl,n-hexadecyloxycarbonyl, n-docosyloxycarbonyl, etc.; as the sulfonamidogroup, e.g., methylsulfonamido, octylsulfonamido, phenylsulfonamido,etc. In formula (I), R₁ and R₂ each may preferably be a straight-chainor branched alkyl or alkenyl group having 1 to 32 carbon atoms. R₃, R₄,R₅ and R₆ each may preferably be hydrogen, straight-chain or branchedalkyl or alkenyl having 1 to 32 carbon atoms, or an alkoxy group having1 to 8 carbon atoms.

Particularly preferable is the case where at least one of R₁ and R₂ isan alkyl group having 8 to 32 carbon atoms; and at least two of R₃, R₄,R₅ and R₆ are an alkyl group (preferably 1 to 8 carbon atoms), analkenyl group (preferably 2 to 8 carbon atoms) or an alkoxy group(preferably 1 to 8 carbon atoms) and the other two groups (particularlyR₄ and R₅) are hydrogen atoms.

The groups and ring appeared in the general formula (I) include thesubstituents which do not substantially react with the oxidized form ofa developer to form a coloring dye as explained before.

Said substituents mean groups containing no active methylene and activemethine groups therein.

Although the substituents may be any substituents, preferred ones areone or more appropriately selected from the group consisting of halogen,hydroxyl, carboxy, sulfo, cyano, alkyl (having preferably 1 to 32 carbonatoms) group, alkenyl (having preferably 2 to 32 carbon atoms) group,alkoxy group, alkylthio group, alkenyloxy group, alkenylthio group, arylgroup, aryloxy group, arylthio group, arylamino group, alkylamino group,alkenylamino group, acyl group, acyloxy group, acylamino group,carbamoyl group, sulfonamido group, sulfamoyl group, alkoxycarbonylgroup, aryloxycarbonyl group and heterocyclic ring (preferably of 5 to 6ring members having nitrogen, oxygen and/or sulfur atoms) among whichhydroxyl, cyano, carboxy, halogen, an aryl group, an alkoxy group having1 to 32 carbon atoms, an aryloxy group and an alkoxycarbonyl grouphaving 1 to 32 carbon atoms are more preferred.

The representative and concrete examples of the compound of thisinvention will be shown below, which, however, should not be construedto restrict the compound used in this invention. ##STR3##

The compounds of this invention can easily be synthesized by the methodsdescribed in Journal of the Chemical Society, pages 2904-2914 (1965) andJournal of Organic Chemistry, vol. 23, pages 75-76.

Examples of syntheses will be illustrated below. These examples show,only for reference, representative and concrete examples of compoundssynthesized by general methods including the synthetic methods describedin the above-mentioned literatures.

Synthesis-1 (Synthesis of exemplified compound No. 4)

In 500 ml of ethanol was dissolved 27.1 g of potassium hydroxide. In theresulting solution were further dissolved 50 g of2-methyl-5-secdodecylhydroquinone and 56 g of butyl bromide, and thesolution was heated under reflux. After two hours, the inorganicsubstance formed was removed by filtration and the solvent was distilledoff from the filtrate. Distillation of the residue gave a productboiling at 158°-162° C./0.2 mmHg.

The product was identified to be the desired one by its boiling point(BP), infrared absorption spectrum (IR), nuclear magnetic resonancespectrum (NMR), mass spectrum (MS) and the result of its elementaryanalysis. The desired product was confirmed to be a mixture of severalisomers.

Elementary Analysis (for C₂₇ H₄₈ O₂) (unit:%): Calcd.: C: 80.14; H:11.96. Found: C: 80.40; H: 12.23.

Synthesis-2 (Synthesis of exemplified compound No. 7)

In 15 l of ethanol was dissolved 843 g of potassium hydroxide, and 2,000g of 2-methyl-5-secoctadecylhydroquinone and 2,460 g of octyl bromidewere added thereto. The resulting mixture was heated for 3.5 hours underreflux with stirring. After reaction, inorganic substances were filteredoff. After evaporating the solvent from the filtrate, the residue wasdistilled under reduced pressure to give a product boiling at 205°-210°C./0.2 mmHg. The product was identified to be the desired one by its BP,IR and the result of its elementary analysis.

Elementary Analysis (for C₄₁ H₇₆ O₂) (unit: %): Calcd.: C: 81.93; H:12.75. Found: C: 82.08; H: 12.91.

Synthesis-3 (Synthesis of exemplified compound No. 8)

In 500 ml of ethanol was dissolved 168.6 g of potassium hydroxide, and400 g of 2-methyl-6-secoctadecylhydroquinone and 492 g of octyl bromidewere dissolved therein. The resulting solution was refluxed underheating with stirring for 4 hours. After reaction, inorganic substancesformed were filtered off. Then the filtrate was condensed by evaporatingthe solvent and the residue was distilled under reduced pressure to givea very viscous substance boiling at 199°-206° C./0.05 mmHg. The productwas identified to be the desired one by means of BP, NMR, IR and theresult of its elementary analysis.

Elementary Analysis (for C₄₁ H₇₆ O₂) (unit: %): Calcd.: C: 81.93; H:12.75. Found: C: 82.11; H: 12.92.

Synthesis-4 (Synthesis of exemplified compound No. 11)

In 2,000 ml of n-hexane was dissolved 2,300 g of2,5-di-dodecyloxytoluene, and 100 ml of concentrated sulfuric acid wasadded thereto. The resulting mixture was heated at 50° C. with stirringand then isobutene was absorbed therein. After completion of thereaction, the n-hexane was removed by distillation under reducedpressure and the residue was washed with methanol to give an oil. Theoil was crystallized by cooling and then recrystallized from acetone togive white needles melting at 40°-41.5° C. The product was identified tobe the desired one by means of its melting point (MP), NMR, IR and theresult of its elementary analysis.

Elementary Analysis (for C₃₅ H₆₄ O₂) (unit: %): Calcd.: C: 81.33; H:12.48. Found: C: 81.51; H: 12.64.

Synthesis-5 (Synthesis of exemplified compound No. 16)

In 500 ml of ethanol was dissolved 27.1 g of potassium hydroxide, and 50g of 2-methyl-5-secdodecylhydroquinone and 125 g of hexadecyl bromidewere added thereto. The resulting mixture was heated under reflux withstirring. After 2 hours the solvent was removed by distillation and thenthe resulting residue was dissolved in ligroin. After removing the saltformed by filtration, the ligroin was removed by distillation from thefiltrate. The black residue thus obtained was purified by columnchromatography (silica gel: 200 mesh, developing solvent: n-hexane) togive a light yellow liquid. The product was identified to be the desiredone by means of IR, NMR and the result of its elementary analysis.Further, the desired product was found to be a mixture of severalisomers.

Elementary Analysis (for C₅₁ H₉₆ O₂) (unit: %): Calcd.: C: 82.63; H:13.05. Found: C: 82.89; H: 13.27.

Synthesis-6 (Synthesis of exemplified compound No. 17)

In 10 of ethanol was dissolved 480 g of an aqueous solution of potassiumhydroxide. To the resulting solution were added 500 g oftrimethylhydroquinone and 1,410 g of octyl bromide, and the mixture wasrefluxed under heating for 3.5 hours. After reaction, the ethanol wasremoved from the reaction mixture by distillation, water was added tothe residue and the mixture was extracted with n-hexane. After then-hexane layer was washed with a around-10% aqueous sodium hydroxide andthen with water, the layer was condensed by evaporation under reducedpressure. The residue thus obtained was evaporated under reducedpressure to give a light yellow highly viscous product melting at213°-218° C./3 mmHg. The product was identified to be the desired one bymeans of MP, NMR, IR, MS and the result of its elementary analysis.

Elementary Analysis (for C₂₅ H₄₄ O₂) (unit:%): Calcd.: C: 79.73; H:11.78. Found: C: 79.93; H: 11.87.

Synthesis-7 (Synthesis of exemplified compound No. 23)

In 8 l of ethanol was dissolved 320 g of potassium hydroxide. To theresulting solution were added 640 g of2,5-di-morpholinomethyl-hydroquinone and 960 g of octadecyl bromide, andthe resulting mixture was heated under reflux for 4 hours. Afterreaction, the inorganic substances formed were removed by filtration andthe filtrate was cooled to give white needles melting at 66°-68° C. Theproduct was identified to be the desired one by means of MP, NMR, IR andthe result of its elementary analysis.

Elementary Analysis (for C₅₂ H₉₆ N₂ O₄) (unit: %): Calcd.: C: 76.79; H:11.90; N: 3.44. Found: C: 76.94; H: 11.99; N: 3.47.

Synthesis-8 (Synthesis of exemplified compound No. 53)

In 1,500 ml of ethyl acetate was dissolved 664 g of hydroquinone diethylether, and 600 ml of concentrated sulfuric acid was gradually addedthereto. Further, 740 g of 2-methyl-1-pentene was added thereto and themixture was heated under reflux for 7 hours. Then, the solvent wasremoved from the reaction mixture by distillation and 2,500 ml ofmethanol was added to the resulting liquid to precipitate whitecrystals. The thus obtained crystals were recrystallized to obtain thedesired white needles melting at 76°-77° C. The product was confirmed tobe the desired one by means of MP, NMR, IR, MS and the result of itselementary analysis.

Elementary Analysis (for C₂₂ H₃₈ O₂) (unit: %): Calcd.: C: 78.98; H:11.45. Found: C: 89.21; H: 11.48.

Although a little effect was observed in a compound where R₁ and R₂ ofthe above-mentioned formula (I) each represent an alkyl group and thetotal number of carbon atoms of R₁ and R₂ is not more than 2, the extentof the effect is too low to attain the object of this invention.

The compound of this invention may be incorporated in any layerconstituting a color photographic material. It may preferably beincorporated in yellow-, magenta- and cyan- dye-image-forming layers. Itmay also be incorporated in other layers, for example, a layer adjacentto these dye-image-forming layers.

The color photographic material according to this invention may compriseonly one layer, preferably multiple layers including separate layerswhich individually form yellow, magenta and cyan dye images. Not onlyone layer may be included in each yellow, magenta and cyandye-image-forming layers, but also not less than 2 layers may beincluded therein.

In order to incorporate the compound of this invention in the layer orlayers constituting a color photographic material, the following methodsmay generally be applied.

According to methods described in U.S. Pat. Nos. 2,322,027, 2,801,170,2,801,171, 2,272,191 and 2,304,940, the compounds of formula (I)according to this invention, which are soluble in oil, are preferablydissolved in a high-boiling point solvent, in combination of alow-boiling point solvent, if necessary, together with a low-boilingpoint solvent, and then dispersed and incorporated into a silver halideemulsion. If necessary, couplers, hydroquinone derivatives, ultravioletabsorber and known anti-fading agents for dye images may be addedtogether. In this case, two or more of the compounds of formula (I)according to this invention may be used in combination. Theincorporation method of the compounds of this invention will bedescribed in detail as follows: one or more of the compounds togetherwith couplers, hydroquinone derivatives and an ultraviolet absorberand/or known anti-fading agent for dye images, if necessary, aredissolved in a high-boiling point solvent such as organic acid amides,carbamates, esters, ketones, hydrocarbons and urea derivatives,especially di-n-butyl phthalate, tricresyl phosphate, di-isooctylazelate, di-n-butyl sebacate, tri-n-hexyl phosphate, decalin,N,N-diethyl-caprylamidobutyl, N,N-di-ethyl laurylamide,n-pentadecylphenyl ether or a fluorinated paraffin; or, if necessary, ina low-boiling point solvent such as ethyl acetate, butyl acetate, butylpropionate, cyclohexanol, cyclohexane or tetrahydrofuran (thesehigh-boiling and low-boiling point solvents may be used singly or incombination); and the solution is then mixed with an aqueous solutioncontaining a hydrophilic binder such as gelatin which comprises ananionic surface active agent such as alkylbenzenesulfonic acid, andalkylnaphthalene sulfonic acid and/or a nonionic surface active agentsuch as solbitan sesquioleate ester and solbitan monolaurate ester andthe resulting mixture is emulsified by means of a high-speed mixer, acolloid mill or an ultra sonic dispersion apparatus and then isincorporated into a hydrophilic colloidal solution.

The thus obtained hydrophilic colloidal solution is coated (afterincorporation of silver halide as mentioned hereinafter, in cases wheresaid hydrophilic colloidal solution is a silver halide emulsion) byvarious methods to prepare a silver halide lightsensitive colorphotographic material. Then, the silver halide light-sensitive colorphotographic material is subjected to photographic processing asmentioned hereinafter to obtain a color photographic material.

Further, the compounds of this invention may also be dispersed easily inaccordance with the dispersion methods described in the specificationsof U.S. Pat. Nos. 2,269,158, 2,852,382, 2,772,168, 3,619,195 and2,801,170, and JLOP Nos. 59942/1976, 59943/1976, 74538/1974, 17637/1975,25132/1976, 110327/1976 and so on, in which methods are used latexsolutions.

Among the compounds of this invention, those which is soluble in analkaline aqueous solution (or in water) may also be added to thehydrophilic colloidal solution after dissolved in an alkaline aqueoussolution (or in water).

The compounds of this invention also show sufficient effect whenincorporated into a color photographic material which was obtained afterphotographic processing of a silver halide light-sensitive colorphotographic material.

It is preferable that the compound of this invention is added to andincorporated in a silver halide emulsion by dispersing it together withlipophilic photographic additives, such as couplers, etc., in accordancewith the method as mentioned above. It is particularly preferable toincorporate it in a green sensitive emulsion layer containing a couplerwhich forms a magenta dye image. The compound of this invention isparticularly effective when it is used with a 5-pyrazolone coupler amongthe couplers which form magenta dye images.

The amount of the present compound to be added is not limited inparticular since the compound is substantially colorless and does nothave bad influence such as coloring pollution and the like. From amainly economical point of view, it is preferable to use it in an amountof 5 to 500 mol.%, more preferably 10 to 50 mol.% against a coupler usedin cases where it is used for a silver halide light-sensitive colorphotographic material containing a coupler. In cases where it is usedfor a silver halide light-sensitive color photographic materialcontaining no coupler, it is preferably used in an amount of 0.1 to 1mole, particularly 0.15 to 0.6 mole per one mole of silver halide.

It is advantageous to prevent the discoloration by an actinic ray ofshort wave length by using an ultraviolet absorber such asthiazolidones, benzotriazoles, acrylonitriles and benzophenones.

It is particularly advantageous to use Tinuvin PS, Tinuvin 320, Tinuvin326, Tinuvin 327 and Tinuvin 328 singly or in combination.

Any coupler which forms dye images can be used for the silver halidelight-sensitive color photographic material of this invention.

As the couplers which forms yellow dye images may be mentioned abenzoylacetanilide coupler, pivaloylacetanilide coupler or atwo-equivalent dye-forming coupler in which the carbon atom at thecoupling site is connected with a substituent (so-called split-offgroup) which can be split off during the coupling reaction. As thecouplers which form magenta dye images may be mentioned a 5-pyrazolonecoupler, a pyrazolotriazole coupler, a pyrazolinobenzimidazole coupler,an indazolone coupler or a two-equivalent magenta-dye-forming couplerhaving a split-off group. As the couplers which form cyan dye images maybe mentioned a phenol coupler, a naphthol coupler, a pyrazoloquinazolonecoupler or a two-equivalent cyan-dye-image-forming coupler.

Representative examples of dye-image-forming couplers used in thisinvention will be shown below, which, however, should not be construedto limit the present invention.

    ______________________________________                                        (Y-1)                                                                               α-(4-carboxyphenoxy)-α-pivalyl-2-chloro-                          5-[γ -(2,4-di-t-amylphenoxy)butylamido]                                 acetonilide                                                             (Y-2)                                                                               α-benzoyl-2-chloro-5-[γ-(2,4-di-t-                                amylphenoxy)butylamido]acetonilide                                      (Y-3)                                                                               α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)                      ethoxycarbonyl]acetanilide                                              (Y-4)                                                                               α-(4-carboxyphenoxy)-α-pivalyl-2-chloro-                          5-[α-(3-pentadecylphenoxy)butyramido]                                   acetanilide                                                             (Y-5)                                                                               α-(1-benzyl-2,4-dioxo-3-imidazolydinyl)-                                α-pivalyl-2-chloro-5-[γ-(2,4-di-t-                                amylphenoxy)butyramido]acetanilide                                      (Y-6)                                                                               α-[4-(1-benzyl-2-phenyl-3,5-dioxo-                                      1,2,4-triazolidinyl)]-α-pivalyl-2-chloro-                               5-[γ-(2,4-di-t-amylphenoxy)butyramido]                                  acetanilide                                                             (Y-7)                                                                               α-acetoxy-α-{3-[α-(2,4-di-t-amylphenoxy)                    butyramido]benzoyl}-2-methoxyacetanilide                                (Y-8)                                                                               α-{3-[α-(2,4-di-t-amylphenoxy)butyramido]                         benzoyl}-2-methoxyacetanilide                                           (Y-9)                                                                               α-[4-(4-benzyloxyphenylsulfonyl)phenoxy]-                               α-pivalyl-2-chloro-5-[γ-(2,4-di-t-                                amylphenoxy)butyramido]acetanilide                                      (Y-10)                                                                              α-pivalyl-α-(4,5-dichloro-3(2H)-pyridazo-                         2-yl)-2-chloro-5-[(hexadecyloxycarbonyl)                                      methoxycarbonyl]acetanilide                                             (Y-11)                                                                              α-pivalyl-α-[4-(p-chlorophenyl)-5-oxo-                            Δ.sup.2 -tetrazolin-1-yl]-2-chloro-5-[α-                          (dodecyloxycarbonyl)ethoxycarbonyl]                                           acetanilide                                                             (Y-12)                                                                              α-(2,4-dioxo-5,5-dimethyloxazolidin-                                    3-yl)-α-pivalyl-2-chloro-5-[α-(2,4-                               di-t-amylphenoxy)butyramido]acetanilide                                 (Y-13)                                                                              α-pivalyl-α-[4-(1-methyl-2-phenyl-3,5-                            dioxo-1,2,4-triazolidinyl)]-2-chloro-                                         5-[γ-(2,4-di-t-amylphenoxy)butyramido]                                  acetanilide                                                             (Y-14)                                                                              α-pivalyl-α-[4-(p-ethylphenyl)-5-oxo-                             Δ.sup.2 -tetrazolyl-1-yl]-2-chloro-5-[γ-                          (2,4-di-t-amylphenoxy)butyramido]                                             acetanilide                                                             (M-1)                                                                               1-(2,4,6-trichlorophenyl)-3-[3-(2,4-                                          di-t-amylphenoxyacetamido)benzamido]-                                         5-pyrazolone                                                            (M-2)                                                                               1-(2,4,6-trichlorophenyl)-3-(3-                                               dodecylsuccinimidobenzamido)-5-pyrazolone                               (M-3)                                                                               4,4'-methylenebis{1-(2,4,6-trichloro-                                         phenyl)-3-[3-(2,4-di-t-amylphenoxy-                                           acetamido)benzamido]-5-pyrazolone}                                      (M-4)                                                                               1-(2,4,6-trichlorophenyl)-3-(2-chloro-                                        5-octadecylsuccinimidoanilino)-5-pyrazolone                             (M-5)                                                                               1-(2-chloro-4,6-dimethylphenyl)-3-{3-                                         [α-(3-pentadecylphenoxy)butyramido]                                     benzamido}-5-pyrazolone                                                 (M-6)                                                                               1-(2,4,6-trichlorophenyl)-3-(2-chloro-                                        5-octadecylcarbamoylamilino)-5-pyrazolone                               (M-7)                                                                               3-ethoxy-1-{4-[α-(3-pentadecylphenoxy)                                  butyramido]phenyl}-5-pyrazolone                                         (M-8)                                                                               1-(2,4,6-trichlorophenyl)-3-(2-chloro-                                        5-tetradecanamidoanilino)-5-pyrazolone                                  (M-9)                                                                               1-(2,4,6-trichlorophenyl)-3-{2-chloro-                                        5-[α-(3-t-butyl-4-hydroxyphenoxy)                                       tetradecanamido]anilino}-5-pyrazolone                                   (M-10)                                                                              1-(2,4,6-trichlorophenyl)-3-[3-(2,4-                                          di-t-amylphenoxyacetamido)benzamido]-                                         4-acetoxy-5-pyrazolone                                                  (M-11)                                                                              1-(2,4,6-trichlorophenyl)-3-[3-(2,4-                                          di-t-amylphenoxyacetamido)benzamido]-                                         4-ethoxycarbonyloxy-5-pyrazolone                                        (M-12)                                                                              1-(2,4,6-trichlorophenyl)-3-[3-(2,4-                                          di-t-amylphenoxyacetamido)benzamido]-                                         4-(4-chlorocinnamoyloxy)-5-pyrazolone                                   (M-13)                                                                              4,4'-benzylidenebis[(1-(2,4,6-trichlorophenyl)-                               3-{2-chloro-5-[γ-(2,4-di-t-amylphenoxy)                                 butyramido]anilino}-5-pyrazolone)]                                      (M-14)                                                                              4,4'-benzylidenebis[(1-(2,3,4,5,6-                                            pentachlorophenyl)-3-{2-chloro-5-[γ-                                    (2,4-di-t-amylphenoxy)butyramido]anilino}-                                    5-pyrazolone)]                                                          (M-15)                                                                              4,4'-(2-chloro)benzylidenebis[1-(2,4,6-                                       trichlorophenyl)-3-(2-chloro-5-                                               dodecylsuccinimidoanilino-5-pyrazolone]                                 (M-16)                                                                              4,4'-methylenebis[(1-(2,4,6-trichlorophenyl)-                                 3-{3-[α-(2,4,-di-t-amylphenoxy)butyramido]                              benzamido}-5-pyrazolone)]                                               (M-17)                                                                              1-(2,6-dichloro-4-methoxyphenyl)-3-                                           (2-methyl-5-acetamidoanilino)-5-pyrazolone                              (M-18)                                                                              1-(2-chloro-4,6-dimethylphenyl)-3-(2-                                         methyl-5-chloroanilino)-5-pyrazolone                                    (M-19)                                                                              1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)-                                 5-pyrazolone                                                            (M-20)                                                                              1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-                                      octadecenylsuccinimido-anilino)-5-                                            pyrazolone                                                              (M-21)                                                                              1-(2,4,6-trichlorophenyl)-3-(2-chloro-                                        tridecanamidoanilino)-5-pyrazolone                                      (C-1)                                                                               1-hydroxy-N-[δ-(2,4-di-t-amylphenoxy)                                   butyl]-2-naphthamide                                                    (C-2)                                                                               2,4-dichloro-3-methyl-6-(2,4-di-t-                                            amylphenoxyacetamido)phenol                                             (C-3)                                                                               2,4-dichloro-3-methyl-6-[α-(2,4-di-t-                                   amylphenoxy)butyramido]phenol                                           (C-4)                                                                               1-hydroxy-4-(3-nitrophenylsulfonamido)-                                       N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-                                    naphthamide                                                             (C-5)                                                                               1-hydroxy-4-[(β-methoxyethyl)carbamoyl]                                  methoxy-N-[δ-(2,4-di-t-amylphenoxy)                                     butyl]-2-naphthamide                                                    (C-6)                                                                               1-hydroxy-4-(isopropylcarbamoyl)methoxy-                                      N-dodecyl-2-naphthamide                                                 (C-7)                                                                               2-perfluorobutyramido-5-[α-(2,4-di-t-                                   amylphenoxy)hexanamido]phenol                                           (C-8)                                                                               1-hydroxy-4-(4-nitrophenylcarbamoyl)                                          oxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-                                  2-naphthamide                                                           (C-9)                                                                               2-(α,α,β,β-tetrafluoropropionamido-                     5-[α-(2,4-di-t-amylphenoxy)butyramido]                                  phenol                                                                  (C-10)                                                                              1-hydroxy-N-dodecyl-2-naphthamide                                       (C-11)                                                                              1-hydroxy-(4-nitro)phenoxy-N-[δ-(2,4-                                   di-t-amylphenoxy)butyl]-2-naphthamide                                   (C-12)                                                                              1-hydroxy-4-(1-phenyl-5-tetrazolyloxy)-                                       N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-                                    naphthamide                                                             (C-13)                                                                              2-(α,α,β,β-tetrafluoropropionamido)-4-                  β-chloroethoxy-5-[α-(2,4-di-t-                                     amylphenoxy)butyramido]phenol                                           (C-14)                                                                              2-chloro-3-methyl-4-ethylcarbamoyl-                                           methoxy-6-[α-(2,4-di-t-amylphenoxy)                                     butyramido]phenol                                                       ______________________________________                                    

The couplers used in light-sensitive silver halide color photographicmaterials according to this invention are usually used within a range of5 to 50 mol.% per silver halide, preferably 10 to 30 mol.%. When used ina developer, they are used in a concentration range of about 0.5 to 3.0g/l, preferably about 1.0 to 2.0 g/l. In these cases, they are usedsingly or in combination of two or more of them and even in the case ofthe combination use, the amount to be added is sufficient enough in theamount described above.

Silver halide emulsion can further comprises hydroquinone derivativeswhich have been well known as antistain agents. Among these hydroquinonederivatives, those having substituted or unsubstituted alkyl group ontheir aromatic nuclei are effective and the most preferred compounds are2,5-dioctylhydroquinone, 2,5-di-tert-amylhydroquinone,2,5-di-tert-butylhydroquinone, etc.

Silver halide emulsions according to this invention are those in whichsilver halide particles are generally dispersed in a hydrophiliccolloid. Silver halides to be used are such as silver chloride, silverbromide, silver iodide, silver chlorobromide, silver iodobromide, silverchloroiodobromide and their mixtures and the silver halide can beprepared by means of various methods such as an ammonia method, aneutralization method, a so-called conversion method, a mixingsimultaneous method, and the like. A hydrophilic colloid used fordispersion of these silver halides are generally gelatin, and/or gelatinderivatives such as phthalated gelatin and malonated gelatin. A part orall parts of the gelatin or gelatin derivative amount can be replacedwith alubumin, agar, gum arabic, arginic acid, casein, partiallyhydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate,polyacrylamide, imidated polyacrylamide, polyvinyl pyrrolidone and/orcopolymer of these vinyl compounds. These silver halide emulsions canoptically be sensitized by using various sensitizing dyes for providingsensitivity in desired sensitive wave length. As preferred sensitizingdyes, there can be used cyanine dyes, merocyanine dyes or complexcyanine dyes in single or in combination. If necessary, the followingphotographic additives can be added to silver halide emulsions in singleor in combination: chemical sensitizers such as thioethers, quatenaryammonium chlorides and polyalkyleneoxide compounds; stabilizers such astriazoles, imidazoles, azaindenes, benzothiazolium compounds, zinccompounds, cadmium compounds, mercaptans; hardeners such as chromiumsalts, zirconium salts, and mucochloric acid, and such hardeners asaldehydes, triazines, polyepoxy compounds, triethylene-phosphonamidesand ethyleneimines; plasticizers of dihydroxyalkanes such as glycerinand 1,5-pentandiol; fluorescent brightening agents; antistatic agents;coating aids. To the silver halide emulsion thus obtained, the compoundhaving formula (I) according to this invention is ordinally dispersed.The so-dispersed emulsion is coated on a base such as cellulose acetatefilms, cellulose nitrate films, synthetic resin films such as films ofpolycarbonate, polyethyleneterephthalate or polystyrene, baryta papers,polyethylene coated papers, glass plate, etc.

The light-sensitive silver halide color photographic material can beeither a coupler-in-emulsion type light sensitive silver halide colorphotographic material which contains couplers in advance and acoupler-out-emulsion type light-sensitive silver halide colorphotographic material which does not contain the coupler in advance butis processed by a developer containing the coupler. It, however, can bepreferably applied to the former type and developed with a colordevelopment after exposure. It also can be a light sensitive silverhalide color photographic material in which both a coupler and a colordeveloping agent are located in the same layer in such a way as not tocontact each other before exposure but to be allowed contact them afterexposure; or a light-sensitive silver halide color photographic materialobtaining a coupler, in which a color developing agent is contained in alayer not containing said coupler, but made in contact with said couplerwhen it is immersed in an alkaline processing solution. In adiffusion-transfer type light-sensitive silver halide color photographicmaterial, the compounds having formula (I) according to this inventioncan be added to sensitive elements and/or receiving elements used forthis kind of photography, preferably to the latter elements. In areversal process, the present photographic material is, after imagewiseexposed, developed with a black and white developing solution, theneither exposed to white light or treated with a bath containing afogging agent such as boron compound and thereafter color-developed withan alkaline developing solution containing a color developing agent. Inthis case, the fogging agent can be contained in the alkaline developingsolution containing the color development agent without trouble. Aftercolor development, the photographic material is bleached with ableaching solution containing ferricyanide or a ferric salt of anaminopolycarboxylic acid as an oxidant and fixed with a fixing solutioncontaining a silver salt solvent such as thiosulfate so as to removesilver image and remained silver halide to remain dye image only.Instead of using both the bleaching and fixing solutions, it can also bebleached and fixed with a combined bleaching and fixing bath which isusually abbreviated as a blix. In combination of the steps of colordevelopment, bleaching, fixing or combined bleaching and fixing, it canalso additionally be processed with various treatments such asprehardening, neutralization, water washing, stopping or stabilization.The preferred developing process of the light-sensitive silver halidecolor photographic material of this invention are, for example, colordevelopment, water washing, if necessary, bleaching and fixing, waterwashing, stabilization, if necessary, and drying in this order. Thisprocessing can be carried out at a high temperature over 30° C. and inan extremely short time. Representative processing and representativecomposition for each processing solution are shown as follows:

    ______________________________________                                        Processing (at 30° C.)                                                                      Processing time                                          ______________________________________                                        Color development    3 min. 30 sec.                                           Bleaching and fixing 1 min. 30 sec.                                           Water washing        2 min.                                                   Stabilization        1 min.                                                   Drying                                                                        Composition of color developing solution:                                     Benzyl alcohol           5.0    ml                                            Sodium hexametaphosphate 2.5    g                                             Anhydrous sodium sulfite 1.9    g                                             Sodium bromide           1.4    g                                             Potassium bromide        0.5    g                                             Borax (Na.sub.2 B.sub.4 O.sub.7 . 10H.sub.2 O)                                                         39.1   g                                             N-ethyl-N-β-methansulfon-                                                amidoethyl-4-aminoaniline                                                     sulfate                  5.0    g                                             Water to make            1      l                                             pH was adjusted to pH 10.30 by using sodium                                   hydroxide.                                                                    Composition of bleaching and fixing solution:                                 Iron ammonium ethylene-                                                       diaminetetraacetate      61.0   g                                             Diammonium ethylenediamine-                                                   tetraacetate             5.0    g                                             Ammonium thiosulfate     124.5  g                                             Sodium metabisulfite     13.3   g                                             Anhydrous sodium sulfite 2.7    g                                             Water to make            1      l                                             pH was adjusted to 6.5 by using ammonia                                       Composition of stabilizer:                                                    Glacial acetic acid      20     ml                                            800 ml of water was added, and the solution                                   was adjusted to pH 3.5 to 4.0 by using                                        sodium acetate and made 1l by water addition.                                 ______________________________________                                    

Useful color developing agents for color development of light-sensitivesilver halide color photographic materials of this invention are such asprimary phenylene diamines, aminophenols, and their derivatives. Therepresentatives are as follows: inorganic acid salts such as salts ofhydrochloric acid and sulfuric acid and organic acid salts such as saltsof p-toluene-sulfonic acid, the salts being ofN,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine,N-carbamidomethyl-N-methyl-p-phenylenediamine,N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine,N-ethyl-N-carboxymethyl-2-methyl-p-phenylenediamine,N-carbamidomethyl-N-ethyl-N-ethyl-2-methyl-p-phenylenediamine,N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminophenol,3-acetylamino-4-aminodimethylaniline,N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline,N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaline,N,N-diethyl-3-methyl-p-phenylenediamine andN-methyl-N-β-sulfoethyl-p-phenylenediamine. These color developingagents are used singly or in the combination of two or more of them.

Light-sensitive silver halide color photographic materials using thecompounds of formula (I) can effectively be processed with a colordeveloping solution containing both a primary aromatic amino type colordeveloping agent and an oxidant which oxidant is to expose metal silverimage to redox reaction.

In the case of using these color developing solutions, the colordeveloping agents are oxidized with an oxidant and form dye images bycoupling with photographic color couplers. Such color developing agentsare disclosed in, for example, JLOP No. 9,729/1973 and preferredoxidants for this object are cobalt complexes having 6 coordinationnumbers. Color processing comprising the use of such color developingsolutions are especially effective for a silver halide light-sensitivecolor photographic material in which a smaller amount of silver thanthat of ordinary light-sensitive silver halide color photographicmaterials is employed for the purpose of saving silver.

Especially useful cobalt complexes contain a ligand selected from thegroup consisting of ethylenediamine, diethylenetriamine,triethylenetetraamine, amine, nitrate, nitrite, azide, chloride,thiocyanate, isothiocyanate, water and carbonate and is further requiredto contain (1) at least two ligants of ethylenediamine, (2) at leastfive ligants of amine, or (3) at least one ligand oftriethylenetetraamine. Especially preferred cobalt complexes are such asfollows:

[Co(En)₂ (N₃)₂ ]X; [Co(En)₂ Cl(NCS)]X; [Co(En)₂ (NH₃)N₃ ]X; [Co(En)₂ Cl₂]X; [Co(En)₂ (SCN)₂ ]X; [Co(En)₂ (NCS)₂ ]X; and [Co(NH₃)₆ ]X.

In the above formulae, "En" represents ethylenediamine and X representsat least one cation selected from the group consisting of chloride,bromide, nitrate, nitrite, perchlorate, acetate, carbonate, sulfite,sulfate, hydrochloride, thiocyanate, isothiocyanate and hydroxide. Mostpreferred complexes are cobalt hexamine salts of such as chloride,bromide, sulfite, sulfate, perchlorate, nitrite and acetate. The amountof cobalt complexes used in a color developing solution is in theconcentration range of about 0.1 to about 50 g, preferably about 1 g toabout 15 g per 1 l of the color developing solution.

Light-sensitive silver halide color photographic materials comprisingcompound of formula (I) according to this invention may also beeffectively processed by a color developing solution containing anaromatic primary amino color developing agent and, if desired, saidcolor developing agent being such as to be received in a sensitive layerduring color development and to be transferred to an amplifying bath andthen contacting the developed materials with the amplifying bathcontaining such oxidant, as described above, for example, a cobaltcomplex having 6 coordination numbers. As a preferred other oxidant forthis object, a hydrogen peroxide aqueous solution which is disclosed inJLOP No. 16,023/1976 can also be effectively used. Silver halidedevelopment inhibitors are preferred to be contained besides oxidants insuch an amplifying solution. By doing so, one is enabled to carry outamplification even under room light. According to this operation, dyeforming can be checked and stopped at a desired dye density. Preferreddevelopment inhibitors are water soluble bromides such as potassiumbromide and heterocyclic compounds such as tetrazole, azaindene andtriazole containing no mercapto group or no ionic iodide.

A concentration of a cobalt complex in an amplifying solution isgenerally in the range of about 0.2 g to about 20 g/l, most preferablyabout 1 g to about 15 g/l and that of the hydrogen peroxide solutionabout 0.01 to 10%, most preferably 0.5 to 5%. In the case of watersoluble bromide as a development inhibitor, it is generally contained inan amount of about 1 g to about 40 g/l in the amplifying solution and adevelopment inhibitor comprising a heterocyclic compound can generallybe used in a concentration of 0.01 g to about 3 g/l. The amplifying bathgenerally can be used in a pH range of 6 to 14, preferably 8 to 12.

To the amplifying solution, there can be contained, besides saiddevelopment inhibitors, if necessary, development accelerators,stabilizers, water softeners, solublizing agents, surfactants,thickeners, agents for preventing the unevenness, etc.

This invention will be illustrated in detail by following examples butis not meant to limit the scope of this invention.

EXAMPLE 1

The respective magenta couplers and the respective exemplified compoundsof this invention (or known compounds) as shown in Table 1-1 weredissolved in the solvent shown in the same Table and 120 mg of2,5-di-t-octylhydroquinone was dissolved therein. The thus obtainedsolution was added to a 5% aqueous gelatin solution containing 2.5 g ofsodium dodecylbenzenesulfonate and then dispersed therein by ahomogenizer. The dispersed liquid thus obtained was added to 1,000 ml ofa green sensitive silver chlorobromide emulsion (silver halide: 40 mol.%), and 10 ml of a 2% methanolic solution ofN,N',N"-triacryloyl-6H-s-triazine was added thereto. Thereafter, theresulting mixture was coated on polyethylene coated paper and dried toobtain a sample of a light-sensitive silver halide color photographicmaterial, which was then wedge-exposed. After processed according to themethod described before, the photographic material was exposed to sunlight for 2 months. Percentage of densities after exposure (referred toas D) against densities before exposure (referred to as Do); that is,D/Do×100 was measured by Sakura color densitometer (manufactured byKonishiroku Photo Ind. Co., Ltd.), as to the rate of resulting dye withgreen light and the Y-stain increasing rate in unexposed part with bluelight. The results were shown in Table 1-2.

                  TABLE 1-1                                                       ______________________________________                                                        anti-fading high-boiling                                                                           low-boiling                              Sam- couplers and                                                                             agents and  solvents and                                                                           solvents &                               ple  their added                                                                              their added their amnts.                                                                           their amnts.                             No.  amounts (g)                                                                              amounts (g) used  (ml) used (ml)                              ______________________________________                                        1     (M-1)  36     --     --   DBP   36   EA   100                           2     "      "      known                                                                         com-                                                                          pound                                                                         (I)    8    "     "    "    "                             3     "      "      known                                                                         com-                                                                          pound                                                                         (IV)   13   "     "    "    "                             4     "      "      exempli-                                                                      fied com-                                                                     pound                                                                         (7)    9.9  "     "    "    "                             5     "      "      exempli-                                                                      fied com-                                                                     pound                                                                         (11)   8.5  "     "    "    "                             6     (M-3)  39     --     --   TPP   39   "    "                             7     "      "      known                                                                         compd                                                                         (III)  6    "     "    "    "                             8     "      "      exemp.                                                                        compd                                                                         (43)   8.4  "     "    "    "                             9     "      "      exemp.                                                                        compd                                                                         (14)   11   "     "    "    "                             10    (M-4)  39     --     --   DBP   19   MA   "                                                             TCP   19                                      11    "      "      known                                                                         compd       DBP   19   "    "                                                 (II)   4.4  TCP   19                                      12    "      "      exemp.                                                                        compd       DBP   19   "    "                                                 (17)   6    TCP   19                                      13    "      "      exemp.                                                                        compd       DBP   19   "    "                                                 (7)    4.8  TCP   19                                                          (8)    4.8                                                14    "      "      exemp.                                                                        compd       DBP   19   "    "                                                 (39)   9.9  TCP   19                                      ______________________________________                                    

DBP: dibutyl phthalate, TCP: tricresyl phosphate,

TPP: triphenyl phosphate, EA: ethyl acetate,

MA: methyl acetate

known compound (I): ##STR4## (a compound described in JLOP No.27333/1976) known compound (II): ##STR5## (a compound described in U.S.Pat. No. 3,432,300) known compound (III): ##STR6## (a compound describedin JLOP No. 14751/1977) known compound (IV): ##STR7## (a compounddescribed in U.S. Pat. No. 2,735,765)

                  TABLE 1-2                                                       ______________________________________                                                                  Y-stain increasing                                  Sample No.                                                                              rate of residual dye                                                                          rate                                                ______________________________________                                        1         30              2,200                                               2         42              1,800                                               3         45              1,700                                               4         65              1,300                                               5         70              1,240                                               6         29              2,300                                               7         35              2,000                                               8         76              1,430                                               9         85              1,360                                               10        42              2,900                                               11        60              2,300                                               12        69              1,560                                               13        76              1,630                                               14        73              1,580                                               ______________________________________                                    

From Table 1-2, the following will be understood: the compound of thisinvention is excellent in the anti-fading effect for a magenta dyeimage, which effect is superior to that of anti-fading agents which havehitherto been known; and the compound of this invention effectivelyprevents a Y-stain in unexposed part and shows an excellent effect overa long period of time.

EXAMPLE 2

The respective yellow couplers and the respective exemplified compoundsof this invention as shown in Table 2-1 were dissolved in the solventshown in the same Table, and 150 mg of 2,5-di-t-octylhydroquinone wasdissolved therein. The obtained solution was added to 500 ml of a 5%aqueous gelatin solution and then dispersed by a homogenizer. Thedispersed liquid thus obtained was added to 1,000 ml of a blue sensitivesilver chlorobromide emulsion (silver chloride: 10 mol. %) and 10 ml ofa 5% methanolic solution of triethylenephosphonamide was added theretoas a hardener. The mixture thus obtained was coated on a polyethylenecoated paper to obtain a sample of a light-sensitive silver halidephotographic material. After processed in the same manner as in Example1, the photographic material was exposed to a xenon fadometer for 100hours. Measurements were conducted in the same manner as in Example 1except that the dye density was measured. The results of Table 2-2 wereobtained.

As seen clearly from Table 2-2, publicly-known compounds do not show anyeffect for preventing the fading of yellow dye images but show rather aneffect for accelerating the fading. On the contrary to that, thecompounds of this invention not only show an excellent effect forpreventing also the fading of yellow dye images but also can preventeffectively the Y-stain in unexposed part.

                  TABLE 2-1                                                       ______________________________________                                                        anti-fading high-boiling                                                                           low-boiling                              Sam- couplers and                                                                             agents and  solvents and                                                                           solvents &                               ple  their added                                                                              their added their amnts.                                                                           their amnts.                             No.  amounts (g)                                                                              amounts (g) used  (ml) used (ml)                              ______________________________________                                        1    (Y-3)   61      --    --   DBP   61   EA   120                           2    "       "      known                                                                         compd.      "     "    "    "                                                  (I)   16                                                 3    "       "      exemp.                                                                        compd.      "     "    "    "                                                 (16)   24.3                                               4    "       "      exemp.                                                                        compd.      "     "    "    "                                                 (25)   29.3                                               5    (Y-5)   76      --    --   "     "    "    "                             6    "       "      known                                                                         compd.      "     "    "    "                                                 (III)  13.4                                               7    "       "      exemp.                                                                        compd.      "     "    "    "                                                 (11)   20                                                 8    "       "      exemp.                                                                        compd.      TCP   "    "    "                                                 (26)   35                                                 ______________________________________                                    

                  TABLE 2-2                                                       ______________________________________                                                                  Y-stain increasing                                  Sample No.                                                                              rate of residual dye                                                                          rate                                                ______________________________________                                        1         57              139                                                 2         56              130                                                 3         70              110                                                 4         71              119                                                 5         89              128                                                 6         60              129                                                 7         93              112                                                 8         95              117                                                 ______________________________________                                    

EXAMPLE 3

In a mixture of 40 g of dibutyl phthalate (DBP) and 120 g of ethylacetate (EA) were dissolved 46 g of a cyan coupler (C-1), 200 mg of2,5-di-t-octylhydroquinone and an anti-fading agent (shown in Table 3with respect to kind and amount to be used). The obtained solution wasadded to 500 ml of a 5% aqueous gelatin solution containing sodiumdodecylbenzenesulfonate and then dispersed by a homogenizer. Thedispersed liquid thus obtained was added to 1,000 ml of a red sensitivesilver chlorobromide emulsion containing 20 mol. % of silver chlorideand then 20 ml of a 4% aqueous solution of sodium2,4-dichloro-6-hydroxy-s-triazine was added thereto as a hardener. Theobtained mixture was coated on a polyethylene coated paper to obtain asample of a light-sensitive silver halide photographic material.Subsequently, a sample was prepared in the same manner as mentionedabove except that 45 g of a cyan coupler (C-3) was used in place of 46 gof a cyan coupler (C-1). After processed in the same manner as inExample 1, these samples were exposed to sun light for 2 weeks.Measurements of the dye densities were conducted in the same manner asin Example 1 except that a red light was used. The results were shown inTable 3.

As is clear from Table 3, it will be understood that the compounds ofthis invention show better effect for preventing the discoloration ofcyan images as compared with known anti-fading agents for dye images.

                  TABLE 3                                                         ______________________________________                                                             rate of                                                                       residual dye                                             anti-fading agents & cyan coupler                                             their amounts added (g)                                                                            C-1       C-3                                            ______________________________________                                        1       --               80        87                                         2       exemplified compd.                                                            (7)           16     90      93                                       3       exemplified compd.                                                            (25)          23.7   92      92                                       4       known compd.                                                                  (I)           12.9   81      88                                       5       known compd.                                                                  (II)          7.3    82      88                                       6       known compd.                                                                  (III)         9      83      86                                       ______________________________________                                    

EXAMPLE 4

Each of the following layers was coated in turn on a polyethylene coatedpaper to prepare a sample of a light-sensitive silver halidephotographic material.

(Sample 1)

First layer:

A blue sensitive silver halide emulsion layer comprising a silverchlorobromide emulsion containing 10 mol. % of silver chloride, whichemulsion contains 400 g of gelatin per mole of silver halide; wassensitized by using 2.5×10⁻⁴ mole of a sensitizing dye of the followingformula: ##STR8## per mole of silver halide; contains 2×10⁻¹ mole of ayellow coupler (Y-6) dissolved and dispersed in DBP per mole of silverhalide; and was coated on a support so that the amount of silver may be400 mg/m².

Second layer:

A gelatin layer which was coated so that the thickness of the dry layermay be 1μ.

Third layer:

A green sensitive silver halide emulsion layer comprising a silverchlorobromide emulsion containing 40 mol. % of silver chloride, whichemulsion contains 500 g of gelatin per mole of silver halide; has beensensitized by using 2.5×10⁻⁴ mole of a sensitizing dye of the followingformula: ##STR9## per mole of silver halide; contains 2×10⁻¹ mole of amagenta coupler (M-14) dissolved and dispersed in TCP per mole of silverhalide; and has been coated so that the amount of silver may be 350mg./m².

Fourth layer:

A gelatin layer having a thickness of 1μ. and containing 30 mg./m² of2,5-di-t-octylhydroquinone dissolved and dispersed in DBP and 700 mg/m²of 2-(2'-hydroxy-3', 5'-di-t-butylphenyl)benzotriazole

Fifth layer:

A red sensitive silver halide emulsion layer comprising a silverchlorobromide emulsion containing 20 mol. % of silver halide, whichemulsion contains 500 g of gelatin per mole of silver halide; has beensensitized by using 2.5×10⁻⁴ mole of a sensitizing dye of the followingformula: ##STR10## per mole of silver halide; contains 2×10⁻¹ mole of acyan coupler (C-3) dissolved and dispersed in TCP per mole of silverhalide; and has been coated so that the amount of silver may be 500mg/m².

Sixth layer:

A gelatin layer of 1μ in dry thickness has been coated (protectivelayer).

Each of the silver halide emulsions used in the first, third and fifthlayers was prepared according to the method described in Japanese PatentPublication No. 7772/1971; subjected to chemical sensitization by usingsodium thiosulfate pentahydrate; and incorporated with4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer, bis(vinylsulfonylmethyl)ether as a hardener and saponin as a coating aid.

To each of the first, third and fifth light-sensitive layer was addedthe compound (exemplified compound No. 16) of the present invention inan amount of 30 mol. % against the coupler contained in each layer anddispersed to prepare Sample 2.

In place of the exemplified compound of this invention which was used inthe preparation of Sample 2 above, the same amount of each knowncompounds (I), (II) and (III) was used to prepare Samples 3, 4 and 5,respectively.

To the third light-sensitive layer of Sample 1 was added a coupler andcompounds No. 10 to 26 in an amount of 30 mol. % against the coupler anddispersed to prepare Samples 6 and 7, respectively.

In place of the exemplified compound of this invention which was used inSample 6, the same amount of known compound (I), (II) or (III) was usedto prepare Samples 8, 9 and 10, respectively.

Each of the Samples as prepared above was wedge-exposed to a blue, greenor red light and processed according to the procedure in Example 1.After exposure for 300 hours, the dye densities and the Y-stainincreasing rates were measured with xenon fadometer. The resultsobtained were shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Sample  rate of residual dye                                                                             Y-stain increas-                                   No.     yellow   magenta   cyan  ing rate                                     ______________________________________                                        1       65       45        70    410                                          2       85       90        89    200                                          3       65       55        68    320                                          4       50       70        70    290                                          5       64       50        67    380                                          6       66       90        71    220                                          7       65       92        71    210                                          8       64       53        71    330                                          9       66       66        69    300                                          10      65       48        70    390                                          ______________________________________                                    

As is clear from Table 4, it will be understood that known anti-fadingagents for dye images do not show any anti-fading effect on dye imagesexcept for magenta dye image at all, or tend to accelerate the fadingand that, on the contrary, the compounds of this invention show anexcellent effect not only for magenta dye images but also for yellow andcyan dye images, and thus the compounds of this invention are extremelyexcellent anti-fading agents for dye images.

EXAMPLE 5

In a mixture of ll g of DBP and 30 g of EA was dissolved 12 g (30 mol. %against the coupler) of Compd. No. 24. The resulting solution was addedto 120 ml of a 5% aqueous gelatin solution containing sodiumdodecylbenzenesulfonate and then dispersed by a homogenizer. Thedispersed liquid thus obtained was added to 300 ml of a green sensitivesilver chlorobromide emulsion (silver chloride: 30 mol. %), coated on apolyethylene coated paper and dried to obtain a sample of alight-sensitive silver halide photographic material.

The color photographic material was wedge-exposed by means of asensitometry method and processed in the following order at 24° C.:

    ______________________________________                                        Processing        min.                                                        ______________________________________                                        First development 5                                                           Water washing     4                                                           Exposure                                                                      Color development 3                                                           Water washing     4                                                           Bleaching         4                                                           Fixing            4                                                           Water washing     10                                                          ______________________________________                                    

In the above first development, color development, bleaching and fixing,the following compositions were employed:

    ______________________________________                                        First development composition:                                                Anhydrous sodium bisulfite                                                                          8.0     g                                               Phenidone             0.35    g                                               Anhydrous sodium sulfite                                                                            37.0    g                                               Hydroquinone          5.5     g                                               Anhydrous sodium carbonate                                                                          28.2    g                                               Sodium thiocyanate    1.38    g                                               Anhydrous sodium bromide                                                                            1.30    g                                               Potassium iodide (0.1%                                                        aqueous solution)     13.0    ml                                              Water to make         1       l (pH 9.9)                                      Color developer composition:                                                  Anhydrous sodium sulfite                                                                            10.0    g                                               N,N-diethyl-p-phenylene-                                                      diamine hydrochloride 3.0     g                                               Magenta coupler (M-19)                                                                              1.5     g                                               Water to make         1       l                                               pH 11.5 with sodium hydroxide                                                 Bleaching solution composition:                                               Anhydrous sodium bromide                                                                            43.0    g                                               Potassium ferricyanide                                                                              165.0   g                                               Borax (Na.sub.2 B.sub.4 O.sub.7 . 10H.sub.2 0)                                                      1.2     g                                               Water to make         1       l                                               Fixing solution composition:                                                  Sodium thiosulfate                                                            pentahydrate          200     g                                               Anhydrous sodium sulfite                                                                            10.0    g                                               Anhydrous bisodium phosphate                                                                        15.0    g                                               Water to make         1       l                                               ______________________________________                                    

The color photographic material so processed was tested in the same wayas in Example 1 except for exposure for 100 hours with a xenon fadometerto measure a rate of residual dye and a Y-stain increasing rate. Forcomparison, known compound (III) was used in the same amount in place ofthe compound of this invention and no compound of this invention wasused in the blank.

The results obtained were listed in Table 5.

                  TABLE 5                                                         ______________________________________                                        Sample  anti-fading rate of      Y-stain increas-                             No.     agent       residual dye ing rate                                     ______________________________________                                        1       Blank       64           485                                          2       exemplified                                                                   compound (24)                                                                             95           110                                          3       known com-                                                                    pound (III) 86           160                                          ______________________________________                                    

From Table 5 above, it will be understood that the compound of thisinvention prevents a Y-stain even in the case where a coupler is notincorporated in a light-sensitive silver halide photographic material(i.e., coupler-in-developer type light-sensitive silver halidephotographic material) and shows an excellent anti-fading effect.

EXAMPLE 6

To a mixture of 20 ml of DBP and 40 ml of EA was added 20 g of therespective anti-fading agent for dye images shown in Table 6. Thesolution was added to a mixture of 2,000 ml of a 10% aqueous gelatin and200 ml of a 5% aqueous sodium dodecylbenzenesulfonate, and thendispersed with a homogenizer. After the dispersed liquid thus obtainedwas coated on a polyethylene coated paper and dried, the existence ofthe precipitation of crystals on the sample thus obtained was checkedwith an optical microscope.

The results were shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Sample    anti-fading agent                                                                              precipitation                                      No.       for dye image    of crystals                                        ______________________________________                                        1         known compd  (V)     Yes                                            2         exemplified                                                                   compound     (1)     No                                             3         exemplified                                                                   compound     (7)     No.                                            4         exemplified                                                                   compound     (10)    No                                             5         exemplified                                                                   compound     (29)    No                                             ______________________________________                                    

known compound (V): ##STR11## (a compound described in Japanese PatentPublication No. 20977/1974)

As seen clearly from Table 6, the compounds of this invention show adispersion stability since the samples (No. 2-5) according to thisinvention did not give any precipitation of crystals even after they hadbeen allowed to stand for 2 months.

EXAMPLE 7

In a mixture of 25 ml of DBP and 70 ml of EA was dissolved 36 g of amagenta coupler (M-20) and 11 g of the respective compound of thisinvention listed in Table 7. The resulting solution was added to 500 mlof a 5% aqueous gelatin solution containing 2.5 g of sodiumdodecylbenzenesulfonate, and then dispersed by a homogenizer. Thedispersed liquid thus obtained was added to a green sensitive silverchlorobromide (silver bromide: 80 mol. %) and 10 ml of a 2% methanolicsolution of N,N', N"-triacryloyl-6H-s-triazine as a hardener was addedthereto. The resulting emulsion was coated on a polyethylene coatedpaper and dried. The sample thus obtained was subjected to photographicprocessing, after exposure, in the same way as in Example 1. Thereafter,the sample was subjected to sensitometry in the usual manner by usingSakura-color-densitometer PD-6 (manufactured by Konishiroku PhotoIndustries Co., Ltd.) to measure sensitivity, γ, fog and maximumdensity.

The results were shown in Table 7. Sensitivities are indicated asrelative sensitivities, assuming that the sensitivity of Sample No. 1was 100.

                  TABLE 7                                                         ______________________________________                                                                                maximum                               Sample                                                                              exemplified                       color                                 No.   compounds  sensitivity                                                                              γ                                                                             fog   density                               ______________________________________                                        1     --         100        3.50  0.04  2.85                                  2      (2)       101        3.49  0.03  2.86                                  3     (20)       100        3.51  0.03  2.86                                  4     (36)       100        3.50  0.03  2.85                                  5     (39)       102        3.51  0.03  2.86                                  6     (53)       101        3.50  0.03  2.86                                  ______________________________________                                    

As is clear from Table 7, the compounds of this invention do not affectbadly the photographic characteristics. It is very important that anovel compound does not affect the photographic characteristics when itis added in order to improve other properties than the photographiccharacteristics. In this sense, it will be understood that the compoundsof this invention are excellent photographic additives.

EXAMPLE 8

The respective magenta couplers and the respective compounds of thisinvention or a known anti-fading agent as shown in Table 8-1 weredissolved in the solvent shown in the same Table and 120 mg of2,5-di-t-octylhydroquinone was dissolved therein.

The thus obtained solution was added to a 5% aqueous gelatin solutioncontaining 2.5 g of sodium dodecyl-benzene-sulfonate and then dispersedtherein by a homogenizer. The thus obtained dispersion was added into1,000 cc of a green sensitive silver chloride-bromide emulsion(containing 40 mol. % of silver chloride). 10 ml of 3% aqueous methanolsolution of reaction product of tetrakis (vinyl sulfonyl methyl) methaneand potassium 2-amino methane sulfonate (mol. ratio 1:1) was addedthereto. Thereafter, the resulting mixture was coated on a paper coveredby polyethylene and then dried to obtain a sample of a light-sensitivesilver halide photographic material.

These samples were exposed to light through an optical wedge accordingto a sensitometry method, and then processed as follows:

    ______________________________________                                        Processing (at 33° C.)                                                                     Processing time                                           ______________________________________                                        1. Color development                                                                              3 min. 30 sec.                                            2. Bleaching and fixing                                                                           1 min. 30 sec.                                            3. Washing          3 min. 30 sec.                                            ______________________________________                                        Composition of color developing solution:                                     ______________________________________                                        Benzyl alcohol           15     ml                                            Sodium hexamethaphosphate                                                                              2.5    g                                             Anhydrous sodium sulfite 1.9    g                                             Sodium bromide           1.4    g                                             Potassium bromide        0.5    g                                             Borax (Na.sub.2 B.sub.4 O.sub.7 . 10H.sub.2 O)                                                         39.1   g                                             N-ethyl-N-β-methane                                                      sulfonamide ethyl-3-                                                          methyl-4-amino-aniline                                                        sulfate                  4.5    g                                             Whitex BB (50% solution) 2      ml                                            (Trade name by Sumitomo                                                       Chem. Co.)                                                                    Water to make            1      l                                             pH was adjusted to pH 10.2 by                                                 using sodium hydroxide                                                        ______________________________________                                        Composition of bleaching and fixing solution:                                 ______________________________________                                        The composition was as set forth before.                                      ______________________________________                                    

The thus processed samples were exposed to sun light through transparentwindow glass for three months. Measurements were conducted in the samemanner as Example 1. The results of Table 8-2 were obtained.

From Table 8-2, the following will be understood: the compounds of thisinvention are excellent in the anti-fading effect for a magenta dyeimage, which effect is superior to that of known anti-fading agents: andthe compounds of this invention effectively prevent a Y-stain inunexposed part.

                  TABLE 8-1                                                       ______________________________________                                                                    high-boiling                                                                           low-boiling                                    couplers and                                                                             anti-fading                                                                              solvents and                                                                           solvents &                               Sample                                                                              their added                                                                              agents and their amnts.                                                                           their amnts.                             No.   amounts (g)                                                                              amounts (g)                                                                              used (ml)                                                                              used (ml)                                ______________________________________                                        1     M-20    39     --       DBP   39   EA   80                              2     "       "      known cmpd.                                                                   (IV) 13.0                                                                              "     "    "    "                               3     "       "      exemp. cmpd.                                                                  (51) 9.3 "     "    "    "                               4     "       "      exemp. cmpd.                                                                  (55) 7.0 "     "    "    "                               5     "       "      exemp. cmpd. -      (65) 7.9                                                                           " " " "                         ______________________________________                                    

                  TABLE 8-2                                                       ______________________________________                                                                   Y-stain increas-                                   Sample No.                                                                              rate of residual dye                                                                           ing rate                                           ______________________________________                                        1         45               2,000                                              2         57               1,850                                              3         70               1,200                                              4         77               1,250                                              5         75               1,000                                              ______________________________________                                    

We claim:
 1. A color photographic material comprising a support and ahydrophilic layer containing a dye image which material contains acompound represented by the following formula (I): ##STR12## wherein R₁and R₂ each represent an alkyl group, an alkenyl group, a cycloalkylgroup, an aryl group or a heterocyclic ring, and when R₁ and R₂ both arean alkyl group, the sum of the carbon atoms of said alkyl group is notless than 3; two of R₃, R₄, R₅ and R₆ represent an alkyl, alkenyl oralkoxy group of up to 32 carbon atoms and the other two representhydrogen; and each of said compound does not substantially react withthe oxidized form of a developer to form a coloring dye.
 2. A colorphotographic material according to claim 1 wherein the hydrophilic layercontaining the compound.
 3. A color photographic material according toclaim 1 wherein the photographic material further comprises a layeradjacent to the hydrophilic layer, the adjacent layer containing thecompound.
 4. A color photographic material according to claim 1 whereinR₁ and R₂ each represent an alkyl group having 1 to 32 carbon atoms oran alkenyl group having 2 to 32 carbon atoms.
 5. A color photographicmaterial according to claim 1 wherein two of R₃, R₄, R₅ and R₆ eachrepresent an alkyl group having 1 to 8 carbon atoms, an alkenyl grouphaving 2 to 8 carbon atoms or an alkoxy group having 1 to 8 carbonatoms.